Resin composition for semiconductor package, prepreg, and metal clad laminate using the same

ABSTRACT

The present invention relates to a resin composition having high miscibility between internal components, low thermal expansion characteristics, and excellent mechanical properties, and a prepreg and a metal clad laminate formed from the same.

This application is a National Phase entry pursuant to 35 U.S.C. § 371of International Application No. PCT/KR2018/002780 filed on Mar. 8,2018, and claims the benefit of priority from Korean Patent ApplicationNo. 10-2017-0036105 filed on Mar. 22, 2017 and Korean Patent ApplicationNo. 10-2018-0018019 filed on Feb. 13, 2018, the full disclosures ofwhich are incorporated herein by reference.

FIELD

The present invention relates to a resin composition for a semiconductorpackage having high miscibility between internal components, low thermalexpansion characteristics, and excellent mechanical properties, and aprepreg and a metal clad laminate using the same. More specifically, thepresent invention relates to a thermosetting resin composition for asemiconductor package capable of preparing a prepreg and a metal cladlaminate exhibiting excellent physical properties even through a reflowprocess of a printed circuit board (PCB), and a prepreg using the same.

BACKGROUND

A copper clad laminate used in a conventional printed circuit board ismanufactured by impregnating a glass fiber substrate with athermosetting resin varnish, semi-curing the substrate to form aprepreg, and then pressurizing and heating the prepreg together with acopper foil. The prepreg is used for configuring and building up acircuit pattern on the copper clad laminate.

In recent years, as high-performance, thickness reduction, and weightreduction of electronic devices, communication devices, personalcomputers, smartphones, and the like have accelerated, and semiconductorpackages have also been required to be thinner, there has been a growingneed for thinner printed circuit boards for semiconductor packages.

However, the stiffness of the printed circuit board is decreased as aresult of thinning, and warpage of the semiconductor package occurs dueto a difference in thermal expansion rates between the chip and theprinted circuit board. This warpage phenomenon is further aggravated bya phenomenon in which the printed circuit board is not recovered afterrepeatedly applying a high temperature in the PCB reflow process.

Therefore, in order to improve this warpage phenomenon, studies havebeen conducted on techniques for lowering the thermal expansion rate ofa substrate. For example, a technique of filling a prepreg with a highcontent-filler has been proposed. However, filling the prepreg with ahigh content-filler, is limited because of lowering of the flow propertyof the prepreg.

Therefore, there is a need to develop a prepreg and a metal cladlaminate which are capable of achieving a low thermal expansion rate andexcellent mechanical properties while ensuring high miscibility betweenthe filler and the resin.

SUMMARY

It is an object of the present invention to provide a resin compositionfor a semiconductor package having high miscibility between internalcomponents, low thermal expansion characteristics, and excellentmechanical properties.

It is another object of the present invention to provide a prepreg and ametal clad laminate using the thermosetting resin composition for asemiconductor package.

The present invention provides a resin composition for a semiconductorpackage including: an amine curing agent containing one or morefunctional groups selected from the group consisting of a sulfone group,a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbonatoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl grouphaving 2 to 20 carbon atoms, and an alkylene group having 1 to 20 carbonatoms; a thermosetting resin; and an inorganic filler containing a firstinorganic filler having an average particle diameter of 0.1 μm to 100 μmand a second inorganic filler having an average particle diameter of 1nm to 90 nm, wherein the thermosetting resin is contained in an amountof 400 parts by weight or less based on 100 parts by weight of the aminecuring agent, and the alkyl group having 1 to 20 carbon atoms, the arylgroup having 6 to 20 carbon atoms, the heteroaryl group having 2 to 20carbon atoms, and the alkylene group having 1 to 20 carbon atomscontained in the amine curing agent are each independently substitutedwith one or more functional groups selected from the group consisting ofa nitro group, a cyano group, and a halogen group.

The present invention also provides a prepreg obtained by impregnating afiber substrate with the resin composition for a semiconductor package.

In addition, the present invention provides a metal clad laminateincluding: the prepreg; and a metal foil integrated with the prepreg byheating and pressurizing.

Hereinafter, a resin composition for a semiconductor package accordingto a specific embodiment of the present invention, and a prepreg and ametal clad laminate using the same, will be described in detail.

DETAILED DESCRIPTION

According to one embodiment of the present invention, a resincomposition for a semiconductor package including: an amine curing agentcontaining one or more functional groups selected from the groupconsisting of a sulfone group, a carbonyl group, a halogen group, analkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20carbon atoms, and an alkylene group having 1 to 20 carbon atoms; athermosetting resin; and an inorganic filler containing a firstinorganic filler having an average particle diameter of 0.1 μm to 100 μmand a second inorganic filler having an average particle diameter of 1nm to 90 nm, wherein the thermosetting resin is contained in an amountof 400 parts by weight or less based on 100 parts by weight of the aminecuring agent, and the alkyl group having 1 to 20 carbon atoms, the alkylgroup having 1 to 20 carbon atoms, and the alkylene group having 1 to 20carbon atoms contained in the amine curing agent are each independentlysubstituted with one or more functional groups selected from the groupconsisting of a nitro group, a cyano group, and a halogen group may beprovided.

The present inventors have found that, when the resin composition for asemiconductor package of the one embodiment is used, the reactivity ofthe amine curing agent can be reduced through an amine curing agentcontaining a strong electron withdrawing group (EWG) such as one or morefunctional groups selected from the group consisting of a sulfone group,a carbonyl group, a halogen group, a substituted alkyl group having 1 to20 carbon atoms, a substituted aryl group having 6 to 20 carbon atoms, asubstituted heteroaryl group having 2 to 30 carbon atoms, and asubstituted alkylene group having 1 to 20 carbon atoms, thereby easilycontrolling the curing reaction of the resin composition.

In particular, in the resin composition for a semiconductor package ofthe one embodiment, as the thermosetting resin is contained in an amountof 400 parts by weight or less based on 100 parts by weight of the aminecuring agent, it is possible to prevent a change in physical propertiesof the thermosetting resin due to the filler charged at a high content,and induce uniform curing of the thermosetting resin at a sufficientlevel without being influenced by the filler, thereby improving thereliability of the finally manufactured product and improving themechanical properties such as toughness.

Conventionally, as in the case where the thermosetting resin iscontained in an amount of 400 parts by weight or less based on 100 partsby weight of the amine curing agent, addition of the amine curing agentin a relatively excessive amount causes problems that the flow propertyand moldability are reduced due to excessive curing of the thermosettingresin. However, even when a specific amine curing agent having decreasedreactivity by including the electron withdrawing group (EWG) asdescribed above is added in an excessive amount, the rapid increase inthe curing rate of the thermosetting resin can be suppressed due to areduction in the reactivity of the curing agent. Therefore, the resincomposition for a semiconductor packages and the prepreg obtainedtherefrom can exhibit a high flow property even during long-termstorage, and have an excellent flow property.

In addition, it was found through experiments that, as two types offillers are mixed and added, the filler can be added with a high contentinto the prepreg, thereby realizing a low coefficient of thermalexpansion, and at the same time improving the flow property of thefiller. Furthermore, during the lamination process, a phenomenon inwhich the thermosetting resin and the filler are separated, that is,miscibility between the resin and the filler, is improved, therebycompleting the present invention.

Specifically, the resin composition for a semiconductor package of theone embodiment may include an amine curing agent containing one or morefunctional groups selected from the group consisting of a sulfone group,a carbonyl group, a halogen group, an alkyl group having 1 to 20 carbonatoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl grouphaving 2 to 30 carbon atoms, and an alkylene group having 1 to 20 carbonatoms. In this case, the alkyl group having 1 to 20 carbon atoms, thearyl group having 6 to 20 carbon atoms, the heteroaryl group having 2 to30 carbon atoms, and the alkylene group having 1 to 20 carbon atomscontained in the amine curing agent may each be independentlysubstituted with one or more functional groups selected from the groupconsisting of a nitro group, a cyano group, and a halogen group.

The one or more functional groups selected from the group consisting ofa sulfone group, a carbonyl group, a halogen group, a substituted alkylgroup having 1 to 20 carbon atoms, a substituted aryl group having 6 to20 carbon atoms, a substituted heteroaryl group having 2 to 30 carbonatoms, and a substituted alkylene group having 1 to 20 carbon atomscontained in the amine curing agent is a strong electron withdrawinggroup (EWG), and the amine curing agent containing the electronwithdrawing group has reduced reactivity as compared with an aminecuring agent not containing the electron withdrawing group, therebyeasily controlling the curing reaction of the resin composition.

Therefore, while controlling the degree of curing reaction of thecomposition by the amine curing agent, a high content-inorganic fillercan be introduced into the prepreg to lower the coefficient of thermalexpansion of the prepreg and at the same time improve the flow propertyof the prepreg, thereby improving the filling property of the circuitpattern.

Specifically, the amine curing agent may include one or more compoundsselected from the group consisting of the following Chemical Formulas 1to 3.

In Chemical Formula 1, A is a sulfone group, a carbonyl group, or analkylene group having 1 to 10 carbon atoms, X₁ to X₈ are eachindependently a nitro group, a cyano group, a hydrogen atom, a halogengroup, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,R₁, R₁′, R₂, and R₂′ are each independently a hydrogen atom, a halogengroup, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, nis an integer of 1 to 10, and

the alkylene group having 1 to 10 carbon atoms, the alkyl group having 1to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and theheteroaryl group having 2 to 20 carbon atoms are each independentlysubstituted with one or more functional groups selected from the groupconsisting of a nitro group, a cyano group, a hydrogen atom, and ahalogen group.

In Chemical Formula 2, Y₁ to Y₈ are each independently a nitro group, acyano group, a hydrogen atom, a halogen group, an alkyl group having 1to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or aheteroaryl group having 2 to 20 carbon atoms, R₃, R₃′, R₄, and R₄′ areeach independently a hydrogen atom, a halogen group, an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms,or a heteroaryl group having 2 to 20 carbon atoms, m is an integer of 1to 10, and the alkyl group having 1 to 6 carbon atoms, the aryl grouphaving 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20carbon atoms are each independently substituted with one or morefunctional groups selected from the group consisting of a nitro group, acyano group, and a halogen group.

In Chemical Formula 3, Z₁ to Z₄ are each independently a nitro group, acyano group, a hydrogen atom, a halogen group, an alkyl group having 1to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or aheteroaryl group having 2 to 20 carbon atoms, R₅, R₅′, R₆, and R₆′ areeach independently a hydrogen atom, a halogen group, an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms,or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl grouphaving 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms,and the heteroaryl group having 2 to 20 carbon atoms are eachindependently substituted with one or more functional groups selectedfrom the group consisting of a nitro group, a cyano group, and a halogengroup.

The alkyl group is a monovalent functional group derived from alkane,and examples thereof include a linear, branched, or cyclic group, suchas methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl,hexyl, and the like.

The alkylene group is a divalent functional group derived from alkane,and examples thereof include a linear, branched, or cyclic group, suchas a methylene group, an ethylene group, a propylene group, anisobutylene group, a sec-butylene group, a tert-butylene group, apentylene group, a hexylene group, and the like. The one or morehydrogen atoms contained in the alkylene group can be substituted withsubstituents, similarly to the alkyl group.

The aryl group is a monovalent functional group derived from arene,which may be, for example, a monocyclic or polycyclic group. Specificexamples of the monocyclic aryl group include, but are not limited to, aphenyl group, a biphenyl group, a terphenyl group, a stilbenyl group,and the like. Examples of the polycyclic aryl group include, but are notlimited to, a naphthyl group, an anthryl group, a phenanthryl group, apyrenyl group, a perylenyl group, a chrycenyl group, and a fluorenylgroup. One or more hydrogen atoms of these aryl groups may besubstituted with substituents, similarly to the alkyl group.

The heteroaryl group is a heterocyclic group containing O, N, or S as aheteroatom, and the carbon number thereof is not particularly limited,but may be from 2 to 30. Examples of the heterocyclic group include, butnot are limited to, a thiophene group, a furan group, a pyrrole group,an imidazole group, a triazole group, an oxazole group, an oxadiazolegroup, a triazole group, a pyridyl group, a bipyridyl group, a triazinegroup, an acrydyl group, a pyridazine group, a quinolinyl group, anisoquinoline group, an indole group, a carbazole group, a benzoxazolegroup, a benzimidazole group, a benzothiazole group, a benzocarbazolegroup, a benzothiophene group, a dibenzothiophene group, a benzofuranylgroup, a dibenzofuranyl group, and the like. One or more hydrogen atomsof these heteroaryl groups may be substituted with substituents,similarly to the alkyl group.

The term “substituted” means that a hydrogen atom bonded to a carbonatom of a compound is changed into another functional group, and aposition to be substituted is not limited as long as the position is aposition at which the hydrogen atom is substituted, that is, a positionat which the substituent can be substituted, and when two or more aresubstituted, the two or more substituents may be the same as ordifferent from each other.

More specifically, the Chemical Formula 1 may include a compoundrepresented by Chemical Formula 1-1 below.

In Chemical Formula 1-1, A, X₁ to X₈, R₁, R₁′, R₂, R₂′, and n have thesame meaning as defined in Chemical Formula 1.

Specific examples of Formula 1-1 include 4,4′-diaminodiphenyl sulfone(in Formula 1-1, A is a sulfone group, X₁ to X₈, R₁, R₁′, R₂, and R₂′are each independently a hydrogen atom, and n is 1),bis(4-aminophenyl)methanone (in Formula 1-1, A is a carbonyl group, X₁,X₂, R₁, R₁′, R₂ and R₂′ are each independently a hydrogen atom, and n is1), 4,4′-(perfluoropropane-2,2-diyl)dianiline (in Formula 1-1, A isperfluoropropane-2,2-diyl, X₁ to X₈, R₁, R₁′, R₂, and R₂′ are eachindependently a hydrogen atom, and n is 1),4,4′-(2,2,2-trifluoroethane-1,1-diyl)dianiline (in Formula 1-1, A is2,2,2-trifluoroethane-1,1-diyl, X₁ to X₈, R₁, R₁′, R₂, and R₂′ are eachindependently a hydrogen atom, and n is 1), and the like.

In addition, Chemical Formula 2 may include a compound represented byChemical Formula 2-1 below.

In Chemical Formula 2-1, Y₁ to Y₈, R₃, R₃′, R₄, R₄′, and m have the samemeaning as defined in Chemical Formula 2.

Specific examples of Formula 2-1 include2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl-4,4′-diamine (in Formula 2-1, Y₁to Y₈ are a halogen group such as fluorine, R₃, R₃′, R₄, and R₄′ areeach independently a hydrogen atom, and m is 1),2,2′-bis(trifluoromethyl)biphenyl-4,4′-diamine (wherein Y₂ and Y₇ areeach independently a trifluoromethyl group, Y₁, Y₃, Y₄, Y₅, Y₆, and Y₈are a hydrogen atom R₃, R₃′, R₄, and R₄′ are each independently ahydrogen atom, and m is 1), and the like.

Further, Chemical Formula 3 may include a compound represented byChemical Formula 3-1 below.

In Chemical Formula 3-1, Z₁ to Z₄, R₅, R₅′, R₆, and R₆′ have the samemeaning as defined in Chemical Formula 3.

Specific examples of Formula 3-1 include2,3,5,6-tetrafluorobenzene-1,4-diamine (in Formula 3-1, Z₁ to Z₄ are ahalogen group such as fluorine, and R₅, R₅′, R₆, and R₆′ are eachindependently a hydrogen atom) and the like.

The content of the thermosetting resin may be 400 parts by weight orless, 150 parts by weight to 400 parts by weight, 180 parts by weight to300 parts by weight, 180 parts by weight to 290 parts by weight, or 190parts by weight to 290 parts by weight, based on 100 parts by weight ofthe amine curing agent. When the amine curing agent or the thermosettingresin is a mixture of two or more types thereof, the content of thethermosetting resin mixture may also be 400 parts by weight or less, 150parts by weight to 400 parts by weight, 180 parts by weight to 300 partsby weight, 180 parts by weight to 290 parts by weight, or 190 parts byweight to 290 parts by weight, based on 100 parts by weight of the aminecuring agent mixture.

If the content of the thermosetting resin is excessively increased tomore than 400 parts by weight based on 100 parts by weight of the aminecuring agent, the physical properties of the thermosetting resin may bechanged due to the filler charged at a high content, and it is difficultfor the thermosetting resin to be uniformly cured to a sufficient leveldue to the influence of the filler. Thus, there is a disadvantage thatthe reliability of the finally manufactured product may be deteriorated,and mechanical properties such as toughness may also be deteriorated.

In this case, the resin composition for a semiconductor package may havean equivalent ratio calculated by the following Mathematical Equation 1,of 1.4 or more, 1.4 to 2.5, 1.45 to 2.5, 1.45 to 2.1, 1.45 to 1.8, or1.49 to 1.75.

Equivalent ratio=Total active hydrogen equivalent weight contained inthe amine curing agent/Total curable functional group equivalent weightcontained in the thermosetting resin  [Mathematical Equation 1]

More specifically, in Mathematical Equation 1, the total active hydrogenequivalent weight contained in the amine curing agent means a valueobtained by dividing the total weight (unit: g) of the amine curingagent by the active hydrogen unit equivalent weight (g/eq.) of the aminecuring agent.

When the amine curing agent is a mixture of two or more types thereof,the values are calculated by dividing the weight (unit: g) for eachcompound by the active hydrogen unit equivalent weight (g/eq.), and byusing the value obtained by totaling the divided values, the totalactive hydrogen unit equivalent weight contained in the amine curingagent according to Mathematical Equation 1 can be determined.

The active hydrogen contained in the amine curing agent means a hydrogenatom contained in the amino group (—NH₂) present in the amine curingagent, and the active hydrogen can form a curing structure throughreaction with the curing functional group of the thermosetting resin.

Further, in Mathematical Equation 1, the total curable functional groupequivalent weight contained in the thermosetting resin means a valueobtained by dividing the total weight (unit: g) of the thermosettingresin by the curable functional unit equivalent weight (g/eq.) of thethermosetting resin.

When the thermosetting resin is a mixture of two or more types thereof,the values are calculated by dividing the weight (unit: g) for eachcompound by the curable functional group unit equivalent weight (g/eq.),and by using the value obtained by totaling the divided values, thetotal curable functional group equivalent weight contained in thethermosetting resin according to Mathematical Equation 1 can bedetermined.

The curable functional group contained in the thermosetting resin meansa functional group forming a curing structure through reaction with theactive hydrogen of the amine curing agent, and the type of the curablefunctional group may vary depending on the type of the thermosettingresin.

For example, when an epoxy resin is used as the thermosetting resin, thecurable functional group contained in the epoxy resin may be an epoxygroup. When a bismaleimide resin is used as the thermosetting resin, thecurable functional group contained in the bismaleimide resin can be amaleimide group.

That is, the fact that the resin composition for a semiconductor packagesatisfies the equivalent ratio calculated by the Mathematical Equation 1of 1.4 or more means that the amine curing agent is contained at such alevel that the curable functional group contained in all thermosettingresins causes a sufficient curing reaction. Therefore, in the resincomposition for a semiconductor package, when the equivalent ratiocalculated by Mathematical Equation 1 decreases to less than 1.4, thephysical property of the thermosetting resin may change due to thefiller charged at a high content, and the thermosetting resin isdifficult to be uniformly cured to a sufficient level due to theinfluence of the filler. Thus, there is a disadvantage that thereliability of the finally manufactured product may be deteriorated, andmechanical properties such as toughness may also be deteriorated.

In addition, the resin composition for a semiconductor package of theone embodiment may include a thermosetting resin.

The thermosetting resin may include at one or more resins selected fromthe group consisting of an epoxy resin, a bismaleimide resin, a cyanateester resin, and a bismaleimide-triazine resin.

In this case, as the epoxy resin, those commonly used for a resincomposition for a semiconductor package can be used without limitation,and the type thereof is not limited and may include one or more selectedfrom the group consisting of a bisphenol A type of epoxy resin, a phenolnovolac type of epoxy resin, a phenyl aralkyl type of epoxy resin, atetraphenyl ethane type of epoxy resin, a naphthalene type of epoxyresin, a biphenyl type of epoxy resin, a dicyclopentadiene type of epoxyresin, and a mixture of a dicyclopentadiene type of epoxy resin and anaphthalene type of epoxy resin.

Specifically, the epoxy resin may include one or more selected from thegroup consisting of a bisphenol A type of epoxy resin represented by thefollowing Chemical Formula 5, a novolac type of epoxy resin representedby the following Chemical Formula 6, a phenylaralkyl type of epoxy resinrepresented by the following Chemical Formula 7, a tetraphenyl ethanetype of epoxy resin represented by the following Chemical Formulas 8, anaphthalene type of epoxy resin represented by the following ChemicalFormulae 9 and 10, a biphenyl type of epoxy resin represented by thefollowing Chemical Formula 11, and a dicyclopentadiene type of epoxyresin represented by the following Chemical Formula 12.

In Chemical Formula 5,

R is

and

n is an integer of 0 or 1 to 50.

More specifically, the epoxy resin of Chemical Formula 5 may be abisphenol-A type of epoxy resin, a bisphenol-F type of epoxy resin, abisphenol-M type of epoxy resin, or a bisphenol-S type of epoxy resin,respectively, depending on the type of R.

In Chemical Formula 6,

R is H or CH₃, and

n is an integer of 0 or 1 to 50.

More specifically, the novolac type of epoxy resin of Chemical Formula 6may be a phenol novolac type of epoxy resin or a cresol novolac type ofepoxy resin, respectively, depending on the type of R.

In Chemical Formula 11,

n is an integer of 0 or 1 to 50.

In Chemical Formula 12, n is an integer of 0 or 1 to 50.

Further, when the resin composition for a semiconductor package containsan epoxy resin, a curing agent of an epoxy resin can be used togethertherewith for curing.

As the curing agent of the epoxy resin, those commonly used for theresin composition for a semiconductor package can be used withoutlimitation, and the type thereof is not limited. For example, a phenolnovolac type, an amine type, a thiol type, an acid anhydride type, andthe like may be mentioned, and these may be used alone or in acombination of two or more types thereof.

Further, as the curing agent of the epoxy resin, those commonly used forthe resin composition for a semiconductor package can be used withoutlimitation, and the type thereof is not limited.

As a preferable example, the bismaleimide resin may be one or moreselected from the group consisting of a diphenylmethane type ofbismaleimide resin represented by the following Chemical Formula 13, aphenylene type of bismaleimide resin represented by the followingChemical Formula 14, a bisphenol A type of diphenyl ether bismaleimideresin represented by the following Chemical Formula 15, and an oligomerof a diphenylmethane type of bismaleimide resin and a phenylmethane typeof bismaleimide resin represented by the following Chemical Formula 16.

In Chemical Formula 13,

R₁ and R₂ are each independently H, CH₃, or C₂H₅.

in Chemical Formula 16,

n is an integer of 0 or 1 to 50.

In addition, as the cyanate ester resin, those commonly used for a resincomposition for a semiconductor package can be used without limitation,and the type thereof is not limited.

As a preferable example, the cyanate ester resin may be a novolac typeof cyanate resin represented by the following Chemical Formula 17, adicyclopentadiene type of cyanate resin represented by the followingChemical Formula 18, a bisphenol type of cyanate resin represented bythe following Chemical Formula 19, and their partially-triazinatedprepolymers. These can be used alone or in a combination of two or moretypes thereof.

In Chemical Formula 17,

n is an integer of 0 or 1 to 50.

In Chemical Formula 18,

n is an integer of 0 or 1 to 50.

In Chemical Formula 19,

R is

More specifically, the cyanate resin of Chemical Formula 19 may be abisphenol-A type of cyanate resin, a bisphenol-E type of cyanate resin,a bisphenol-F type of cyanate resin, or a bisphenol-M type of cyanateresin, respectively, depending on the type of R.

As the bismaleimide-triazine resin, those commonly used for the resincomposition for a semiconductor package can be used without limitation,and the type thereof is not limited.

In addition, the resin composition for a semiconductor package of oneembodiment may include an inorganic filler. As the inorganic filler,those commonly used for the resin composition for a semiconductorpackage can be used without limitation, and the type thereof is notlimited. Specific examples thereof include one or more selected from thegroup consisting of silica, aluminum trihydroxide, magnesium hydroxide,molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina,clay, kaolin, talc, calcined kaolin, calcined talc, mica, short glassfiber, glass fine powder, and hollow glass.

Specifically, the resin composition for a semiconductor package of theone embodiment contains a first inorganic filler having an averageparticle diameter of 0.1 μm to 100 μm, and a second inorganic fillerhaving an average particle diameter of 1 nm to 90 nm. The secondinorganic filler having an average particle diameter of 1 nm to 90 nmmay be contained in an amount of 1 part by weight to 50 parts by weight,5 part by weight to 50 parts by weight, or 20 parts by weight to 50parts by weight, based on 100 parts by weigh of the first inorganicfiller having an average particle diameter of 0.1 μm to 100 μm. When thefirst inorganic filler and the second inorganic filler are mixed andused as described above, it is possible to increase the packing densityand thus the filling ratio by using a small-sized nanoparticle and alarge-sized microparticle together, and also the flow property of theinorganic filler can be increased.

According to a preferred embodiment of the present invention, the firstinorganic filler and the second inorganic filler may be silicas that aresurface-treated with a silane coupling agent from the viewpoint ofimproving moisture resistance and dispersibility.

As a method of surface-treating the inorganic filler, a method oftreating silica particles by a dry method or a wet method using a silanecoupling agent as a surface treatment agent can be used. For example,silica that is surface-treated by a wet method using a silane couplingagent in an amount of 0.01 to 1 part by weight based on 100 parts byweight of silica particles can be used.

Specific examples of the silane coupling agent include an aminosilanecoupling agent such as 3-aminopropyltriethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane, andN-2-(aminoethyl)-3-aminopropyltrimethoxysilane, an epoxy silane couplingagent such as 3-glycidoxypropyltrimethoxysilane, a vinyl silane couplingagent such as 3-methacryloxypropyltrimethoxysilane, a cationic silanecoupling agent such asN-2-(N-vinylbenzylaminoethyl)-3-aminopropyltrimethoxysilanehydrochloride, and a phenylsilane coupling agent. The silane couplingagent can be used alone, or if necessary, at least two silane couplingagents can be used in combination.

More specifically, the silane compound may include aromatic aminosilaneor (meth)acrylsilane. As the first inorganic filler having an averageparticle diameter of 0.1 μm to 100 μm, silicas treated with an aromaticamino silane can be used, and as the second inorganic filler having anaverage particle diameter of 1 nm to 90 nm, silicas treated with a(meth)acryl silane can be used. A specific example of the silicastreated with an aromatic aminosilane includes SC2050MTO (Admantechs). Aspecific example of the silicas treated with (meth)acryl silanesincludes AC4130Y (Nissan Chemical). The (meth)acryl is intended to coverboth acrylic and methacrylic.

The inorganic filler may be dispersed in the resin composition for asemiconductor package. The fact that the inorganic filler is dispersedin the resin composition for a semiconductor package means that theinorganic filler and other components (thermosetting resin or aminecuring agent, etc.) contained in the resin composition for asemiconductor package are mixed without being separated. That is, theresin composition for a semiconductor package of the one embodiment doesnot form a separated phase such as an inorganic filler-separated phasecomposed of two or more inorganic fillers or a resin-separated phasecomposed of a thermosetting resin, but can form a dispersed phase byuniform mixing of the filler and the thermosetting resin. As a result,even when the inorganic filler is filled at a high content, the prepregcan realize an appropriate level of flowability, a low coefficient ofthermal expansion, and a good mechanical properties.

On the other hand, the content of the inorganic filler may be 200 partsby weight or more, 200 parts by weight to 500 parts by weight, or 250parts by weight to 400 parts by weight, based on 100 parts by weight ofthe amine curing agent and the thermosetting resin. When the content ofthe filler is less than about 200 parts by weight, the coefficient ofthermal expansion is increased and thus the warpage phenomenon isaggravated during the reflow process, and the stiffness of the printedcircuit board is reduced.

The resin composition for a semiconductor package of the one embodimentcan be used as a solution by adding a solvent if necessary. If thesolvent exhibits good solubility for the resin component, the typethereof is not particularly limited, and alcohols, ethers, ketones,amides, aromatic hydrocarbons, esters, nitriles, and the like can beused. These can be used alone or a mixed solvent of two or more thereofcan be used. The content of the solvent is not particularly limited aslong as it can cause the resin composition to be impregnated into theglass fiber at the time of producing the prepreg.

In addition, the resin composition of the present invention may furtherinclude various other polymeric compounds such as other thermosettingresins, thermoplastic resins and oligomers and elastomers thereof, andother flame retardant compounds or additives, as long as the inherentcharacteristics of the resin composition are not impaired. These are notparticularly limited as long as they are selected from those that arecommonly used. Examples of the additives include ultraviolet absorbers,antioxidants, photopolymerization initiators, fluorescent brighteningagents, photosensitizers, pigments, dyes, thickeners, lubricants,antifoaming agents, dispersants, leveling agents, and brighteners. Thecomposition can used by mixing them so as to match the purpose.

The resin composition for a semiconductor package of the one embodimentcan have a coefficient of thermal expansion (CTE) of 15 ppm/° C. orless, or 5 ppm/° C. to 15 ppm/° C. Specifically, the coefficient ofthermal expansion means a measured value obtained by a process in whichthe copper foil layer is removed by etching in the state of the copperclad laminate obtained from the resin composition for a semiconductorpackage, a test specimen is prepared in the MD direction, and thenmeasurement is performed from 30° C. to 260° C. at a heating rate of 10°C./min by using TMA (TA Instruments, Q400) to obtain the measured valuein the temperature range of 50° C. to 150° C.

As the resin composition for a semiconductor package has a lowcoefficient of thermal expansion as described above, it can minimize thegeneration of warpage of the semiconductor package caused by adifference in thermal expansion rates between the chip and the printedcircuit board in the process of preparing or building up a metal cladlaminate. Therefore, the metal clad laminate containing the prepreg canbe successfully used for the build-up of the printed circuit board for asemiconductor package.

The resin composition for a semiconductor package of the one embodimentmay have resin flow of 10% to 25%, or 15% to 25%, as measured byIPC-TM-650 (2.3.17). Specifically, the resin flow can be measuredaccording to IPC-TM-650 (2.3.17) using a Carver press in a prepreg stateobtained from the resin composition for a semiconductor package. Sincethe resin composition for a semiconductor package has theabove-mentioned level of resin flow, it is possible to ensure a flowproperty in the process of preparing or building up a metal cladlaminate, so that a fine pattern can be easily filled. Therefore, themetal clad laminate can be successfully used for the build-up of theprinted circuit board for a semiconductor package.

When the resin flow of the resin composition for a semiconductor packageis excessively reduced, the filling of fine patterns decreases duringthe metal lamination and build-up process, resulting in the generationof laminate voids and the reduction of process yield and efficiency.Further, when the resin flow of the resin composition for asemiconductor package is excessively increased, there arises a problemof uneven thickness of the printed circuit board due to excessive resinflow during the lamination process, or the thickness may be thinner thanthe designed thickness, and thus the stiffness can be reduced.

The resin composition for a semiconductor package of the one embodimenthas a minimum viscosity at 140° C. or higher, or 145° C. to 165° C., andthe minimum viscosity may be 100 Pa·s to 500 Pa·s, 150 Pa·s to 400 Pa·S,200 Pa·s to 350 Pa·s, or 250 Pa·s to 320 Pa·s. Specifically, theviscosity can be measured using a modular compact rheometer MCR 302(Anton Paar) in a prepreg state obtained from the resin composition fora semiconductor package. As the resin composition for a package exhibitsthe above-mentioned level of viscosity, the flow property can be ensuredin the process of preparing a metal clad laminate or in a build-upprocess, so that a fine pattern can be easily filled. Therefore, themetal clad laminate can be successfully used for the build-up of theprinted circuit board for a semiconductor package.

Further, the resin composition for a semiconductor package of the oneembodiment may have tensile elongation of 2.0% or more, 2.0% to 5.0%,2.0% to 3.0%, or 2.5% to 3.0%, as measured by IPC-TM-650 (2.4.18.3).Specifically, the tensile elongation can be measured by a process inwhich, in the prepreg state obtained from the resin composition for asemiconductor package, ten sheets are laminated such that the MD and TDdirections of the glass fibers are aligned parallel to each other, andpressed for 100 minutes under conditions of 220° C. and 35 kg/cm², andthen the tensile elongation in the MD direction is measured using aUniversal Testing Machine (Instron 3365) according to IPC-TM-650(2.4.18.3). As the resin composition for a semiconductor packageexhibits the above-mentioned level of viscosity, the flow property canbe ensured in the process of preparing a metal clad laminate or in abuild-up process, so that a fine pattern can be easily filled.Therefore, due to excellent durability, it can be successfully used forthe build-up of the printed circuit board for a semiconductor package.

On the other hand, according to another embodiment of the presentinvention, a prepreg produced by impregnating the resin composition fora semiconductor package into a fiber substrate may be provided.

The prepreg means that the resin composition for a semiconductor packageis impregnated into the fiber substrate in a semi-cured state.

The type of the fiber substrate is not particularly limited, but a glassfiber substrate, a synthetic fiber substrate made of a woven fabric ornon-woven fabric composed mainly of a polyamide-based resin fiber suchas a polyamide resin fiber, an aromatic polyamide resin fiber, or thelike, a polyester-based resin fiber such as a polyester resin fiber, anaromatic polyester resin fiber, a wholly aromatic polyester resin fiberor the like, a polyimide resin fiber, a polybenzoxazole fiber, afluororesin fiber and the like, a paper substrate composed mainly ofkraft paper, cotton linter paper, linter/kraft pulp-mixed paper, and thelike can be used. Preferably, a glass fiber substrate is used. The glassfiber substrate can improve the strength of the prepreg, reduce thewater absorption rate, and reduce the coefficient of thermal expansion.

The glass substrate used in the present invention can be selected fromglass substrates used for various printed circuit board materials.Examples thereof include, but are not limited to, glass fibers such as Eglass, D glass, S glass, T glass, NE glass, and L glass. The glasssubstrate can be selected in accordance with the intended use orperformance, as necessary. The form of the glass substrate is typicallya woven fabric, a nonwoven fabric, a roving, a chopped strand mat, or asurfacing mat. The thickness of the glass substrate is not particularlylimited, but it may be about 0.01 mm to 0.3 mm or the like. Among theabove materials, the glass fiber material is more preferable in terms ofstrength and water absorption characteristics.

In addition, in the present invention, the method for preparing theprepreg is not particularly limited, and may be manufactured by a methodthat is well known in the art. For example, the preparation method ofthe prepreg may be an impregnation method, a coating method usingvarious coaters, a spraying method, or the like.

In the case of the impregnation method, a prepreg can be prepared bypreparing a varnish and then impregnating the fiber substrate with thevarnish.

The preparation conditions of the prepreg are not particularly limited,but it is preferable to use them in a varnish state in which a solventis added to the resin composition for a semiconductor package. Thesolvent for a resin varnish is not particularly limited as long as it ismiscible with the resin component and has good solubility. Specificexamples thereof include ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such asbenzene, toluene, and xylene, amides such as dimethylformamide anddimethylacetamide, and aliphatic alcohols such as methyl cellosolve andbutyl cellosolve.

In addition, it is desirable that the used solvent volatilizes by atleast 80% by weight at the time of preparing the prepreg. Therefore,there is no limitation on the production method, drying conditions,etc., and the drying temperature is about 80° C. to 200° C. The dryingtime is not particularly limited as long as it is in balance with thegelling time of the varnish. The impregnation amount of the varnish ispreferably such that the resin solid content of the varnish is about 30to 80% by weight based on the total amount of the resin solid content ofthe varnish and the substrate.

The prepreg of an alternative embodiment may have a coefficient ofthermal expansion (CTE) of 15 ppm/° C. or less, or 5 ppm/° C. to 15ppm/° C. The details of the coefficient of thermal expansion includesthose described above in the resin composition for a semiconductorpackage of the embodiment.

The prepreg of the alternative embodiment may have a resin flow of 10%to 25%, or 15% to 25%, as measured by IPC-TM-650 (2.3.17). The detailsof the resin flow include those described above with reference to theresin composition for a semiconductor package of the one embodiment.

Further, the prepreg of the alternative embodiment may have a minimumviscosity of 140° C. or higher, or 145° C. to 165° C., and the minimumviscosity may be 100 Pa·s to 500 Pa·s, 150 Pa·s to 400 Pa·s, 200 Pa·s to350 Pa·s, or 250 Pa·s to 320 Pa·s. The details of the viscosity includethose described above with reference to the resin composition for asemiconductor package of the one embodiment.

Further, the prepreg of the alternative embodiment may have tensileelongation of 2.0% or more, 2.0% to 5.0%, 2.0% to 3.0%, or 2.3% to 3.0%,as measured by IPC-TM-650 (2.4.18.3). The details of the tensileelongation include those described above with reference to the resincomposition for a semiconductor package of the one embodiment.

According to another embodiment of the present invention, a metal cladlaminate may be provided, including: the above-mentioned prepreg; and ametal foil integrated with the prepreg by heating and pressurizing.

The metal foil includes: a copper foil; an aluminum foil; a compositefoil having a three-layer structure containing an intermediate layer ofnickel, nickel-phosphorus, a nickel-tin alloy, a nickel-iron alloy,lead, or a lead-tin alloy, and containing copper layers having differentthicknesses on both sides thereof; or a composite foil having atwo-layer structure in which aluminum and a copper foil are combined.

According to a preferred embodiment, the metal foil used in the presentinvention is a copper foil or an aluminum foil, and those having athickness of about 2 μm to 200 μm can be used, but those having athickness of about 2 μm to 35 μm are preferred. Preferably, a copperfoil is used as the metal foil. Further, according to the presentinvention, a composite foil having a three-layer structure containing anintermediate layer of nickel, nickel-phosphorus, a nickel-tin alloy, anickel-iron alloy, lead, a lead-tin alloy, or the like, and containingcopper layers having different thicknesses on both sides thereof; or acomposite foil having a two-layer structure in which aluminum and acopper foil are combined can be used as the metal foil.

The metal clad laminate including the prepreg thus prepared can be usedfor manufacturing a double-sided or multilayer printed circuit boardafter one or more sheets are laminated. In the present invention, themetal clad laminate may be subjected to circuit processing to produce adouble-sided or multi-layer printed circuit board, and the circuitprocessing may be carried out by a method which is commonly used inmanufacturing processes of double-sided or multilayer printed circuitboards.

Advantageous Effects

According to the present invention, a resin composition for asemiconductor package having high miscibility between internalcomponents, low thermal expansion characteristics, and excellentmechanical properties, and a prepreg and a metal clad laminate using thesame, can be provided.

EXAMPLES

Hereinafter, the present invention will be described in more detailthrough examples. However, these examples are presented for illustrativepurposes only, and are not intended to limit the present inventionthereto in any way.

Examples and Comparative Examples: Resin Composition for SemiconductorPackage, Prepreg, and Copper Clad Laminate

(1) Preparation of Resin Composition for Semiconductor Package

In accordance with the compositions shown in Tables 1 and 2 below, eachcomponent was added to methyl ethyl ketone so as to match the solidcontent of 65%, and then the mixture was stirred at a speed of 400 rpmat room temperature for one day to prepare resin compositions forsemiconductor packages (resin varnishes) of Examples 1 to 5 andComparative Examples 1 to 4. Particularly, the specific compositions ofthe resin compositions prepared in Examples 1 to 5 are as described inTable 1 below, and specific compositions of the resin compositionsprepared in Comparative Examples 1 to 4 are as described in Table 2below.

(2) Preparation of Prepreg and Copper Clad Laminate

The resin compositions (resin varnishes) for a semiconductor packageprepared above were impregnated into glass fiber (T-glass #1017,manufactured by Nittobo) having a thickness of 15 μm, and then hotair-dried at a temperature of 170° C. for 2 to 5 minutes to prepare aprepreg having a thickness of 25 μm.

Two sheets of the prepregs prepared above were laminated, and then acopper foil (12 μm in thickness, manufactured by Mitsui) was positionedand laminated on both sides thereof and cured for 100 minutes under theconditions of 220° C. and 35 kg/cm².

TABLE 1 Composition of the resin compositions for semiconductor packageof examples Example 1 Example 2 Example 3 Example 4 Example 5 Class(unit: g) (unit: g) (unit: g) (unit: g) (unit: g) Epoxy resin XD-1000 2020 — — — (Epoxy unit equivalent weight: 253 g/eq.) NC-3000H 48 48 — 4865.5 (Epoxy unit equivalent weight: 290 g/eq.) HP-6000 — — 60 20 —(Epoxy unit equivalent weight: 250 g/eq.) Bismaleimide BMI-2300 6.2 6.26.2 6.2 6.2 (Maleimide unit equivalent weight: 179 g/eq.) Amine curingDDS 25.8 25.8 — 25.8 28.3 agent (Active hydrogen unit equivalent weight:62 g/eq.) TFB — — 33.8 — — (Active hydrogen unit equivalent weight: 80g/eq.) DDM — — — — — (Active hydrogen unit equivalent weight: 49.5g/eq.) DDE — — — — — (Active hydrogen unit equivalent weight: 50 g/eq.)Inorganic SC2050MTO 190 234 176 215 190 filler AC4130Y 10 26 44 15 10Equivalent ratio (ratio of amine curing agent 1.49 1.49 1.54 1.49 1.75equivalent weight to thermosetting resin equivalent weight) * DDS:4,4′-diaminodiphenyl sulfone * TFB: 2,2′-bis(trifluoromethyl)benzidine;2,2′-bis(trifluoromethyl)-4,4′-biphenyldiamine * DDM:4,4′-diaminodiphenyl methane * DDE: 4,4′-diaminodiphenyl ether *XD-1000: Epoxy resin (Nippon Kayaku) * NC-3000H: Epoxy resin (NipponKayaku) * HP-6000: Naphthalene-based epoxy resin (DIC Corporation) *BMI-2300: Bismaleimide resin (DAIWA KASEI) * SC2050MTO: Phenylaminosilane-treated slurry type of microsilica, average particle diameter of0.5 μm (Admantechs) * AC4130Y: Methacryl silane-treated slurry type ofnanosilica, average particle diameter of 50 nm (Nissan Chemical) *Equivalent ratio: Calculated through Mathematical Equation 1 below.[Mathematical Equation 1] Equivalent Ratio of Amine Curing Agent toThermosetting Resin = (Total Active Hydrogen Equivalent Weight of DDS +Total Active Hydrogen Equivalent Weight of TFB + Total Active HydrogenEquivalent Weight of DDM + Total Active Hydrogen Equivalent Weight ofDDE)/{(Total Epoxy Resin Equivalent Weight of XD-1000 + Total EpoxyResin Equivalent Weight of NC-3000H + Total Epoxy Resin EquivalentWeight of HP-6000) + (Total Maleimide Equivalent Weight of BMI-2300)}

In Mathematical Equation 1, the total active hydrogen equivalent weightof DDS is a value obtained by dividing the total weight (g) of DDS bythe active hydrogen unit equivalent weight of DDS (62 g/eq.),

the total active hydrogen equivalent weight of TFB is a value obtainedby dividing the total weight (g) of TFB by the active hydrogen unitequivalent weight of TFB (80 g/eq.),

the total active hydrogen equivalent weight of DDM is a value obtainedby dividing the total weight (g) of DDM by the active hydrogen unitequivalent weight of DDM (49.5 g/eq.),

the total active hydrogen equivalent weight of DDE is a value obtainedby dividing the total weight (g) of DDE by the active hydrogen unitequivalent weight of DDE (50 g/eq.),

the total epoxy equivalent weight of XD-1000 is a value obtained bydividing the total weight (g) of XD-1000 by the epoxy unit equivalentweight of XD-1000 (253 g/eq.),

the total epoxy equivalent weight of NC-3000H is a value obtained bydividing the total weight (g) of NC-3000H by the epoxy unit equivalentweight of NC-3000H (290 g/eq.),

the total epoxy equivalent weight of HP-6000 is a value obtained bydividing the total weight (g) of HP-6000 by the epoxy unit equivalentweight of HP-6000 (250 g/eq.), and

the total maleimide equivalent weight of BMI-2300 is a value obtained bydividing the total weight (g) of BMI-2300 by the maleimide unitequivalent weight of BMI-2300 (179 g/eq.).

TABLE 2 Composition of the resin compositions for semiconductor packageof comparative examples Comparative Comparative Comparative ComparativeExample 1 Example 2 Example 3 Example 4 Class (unit: g) (unit: g) (unit:g) (unit: g) Epoxy resin XD-1000 20 20 — 80 (Epoxy unit equivalentweight: 253 g/eq.) NC-3000H 48 48 48 — (Epoxy unit equivalent weight:290 g/eq.) HP-6000 — — 20 — (Epoxy unit equivalent weight: 250 g/eq.)Bismaleimide BMI-2300 6.2 6.2 6.2 6.2 (Maleimide unit equivalent weight:179 g/eq.) Amine curing DDS — — — 13.8 agent (Active hydrogen unitequivalent weight: 62 g/eq.) TFB — — — — (Active hydrogen unitequivalent weight: 80 g/eq.) DDM 25.8 25.8 — — (Active hydrogen unitequivalent weight: 49.5 g/eq.) DDE — — 25.8 — (Active hydrogen unitequivalent weight: 50 g/eq.) Inorganic filler SC2050MTO 200 260 230 234AC4130Y — — — 26 Equivalent ratio (ratio of amine 1.87 1.87 1.84 0.63curing agent equivalent weight to thermosetting resin equivalent weight)*DDS: 4,4′-diaminodiphenyl sulfone *TFB:2,2′-bis(trifluoromethyl)benzidine;2,2′-Bis(trifluoromethyl)-4,4′-biphenyldiamine *DDM:4,4′-diaminodiphenyl methane *DDE: 4,4′-diaminodiphenyl ether *XD-1000:Epoxy resin (Nippon Kayaku) *NC-3000H: Epoxy resin (Nippon Kayaku)*HP-6000: Epoxy resin (DIC Corporation) *BMI-2300: Bismaleimide-basedresin (DAIWA KASEI) *SC2050MTO: Phenylamino silane-treated slurry typeof microsilica, average particle diameter of 0.5 μm (Admantechs)*AC4130Y: Methacryl silane-treated slurry type of nanosilica, averageparticle diameter of 50 nm (Nissan Chemical) *Equivalent ratio:Calculated through the same Mathematical Equation 1 as in Table 1.

Experimental Example: Measurement of Physical Properties of ResinComposition for Semiconductor Package, Prepreg, and Copper Clad LaminateObtained in Examples and Comparative Examples

The physical properties of resin compositions for a semiconductorpackage, prepregs, and copper clad laminates obtained in the examplesand comparative examples were measured by the following methods, and theresults are shown in Table 3 below.

1. Coefficient of Thermal Expansion (CTE)

The copper foil layers of the copper clad laminates obtained in theexamples and comparative examples were removed by etching, and then testspecimens were prepared in the MD direction. The measurement wasperformed from 30° C. to 260° C. at a heating rate of 10° C./min byusing TMA (TA Instruments, Q400), and the measured value in atemperature range of 50° C. to 150° C. was recorded as the coefficientof thermal expansion.

2. Resin flow (RF)

(1) Initial Resin Flow

In the prepreg state obtained in the examples and comparative examples,RF was measured according to IPC-TM-650 (2.3.17) using Carver press(Carver, Inc., #3893. 4NE0000).

(2) Resin Flow after One Month

According to IPC-TM-650 (2.3.17), the prepregs obtained in the Examplesand Comparative Examples were stored at room temperature for one month,and RF was measured using a Carver press (Carver, Inc., #3893.4NE0000).

3. Miscibility

In the copper clad laminates obtained in the examples and comparativeexamples, the copper foil layer on one side thereof was removed byetching, and then the surface of the prepreg was observed with anoptical microscope to confirm whether or not the separation between theresin and the inorganic filler occurred. The miscibility was evaluatedunder the following criteria.

◯: Separation between the resin and the inorganic filler did not occur

X: Separation between the resin and the inorganic filler did occur

4. Viscosity

For the prepregs obtained in the examples and comparative examples, theviscosity was evaluated by measuring it using a rheometer (Anton Paar,Modular Compact Rheometer MCR 302) under the conditions of a temperaturerange of 50° C. to 200° C. and a heating rate of 5° C./min, a normalforce of 5 N, a frequency of 10 Hz, and an amplitude of 0.5%, and thetemperature indicating the minimum viscosity, and the minimum viscosity,were recorded.

5. Measurement of Tensile Elongation

10 sheets of the prepregs obtained in the examples and comparativeexamples were laminated in such a manner that the MD and TD directionsof the glass fibers were aligned parallel to each other, and pressed for100 minutes under the conditions of 220° C. and 35 kg/cm², and then thetensile elongation in the MD direction was measured using a UniversalTesting Machine (Instron 3365) according to IPC-TM-650 (2.4.18.3).

TABLE 3 Results of Experimental Examples Viscosity Minimum Temperatureat the Tensile CTE Resin flow viscosity minimum viscosity elongationClass (ppm/° C.) (%) Miscibility (Pa · s) (° C.) (%) Example 1 10.5 23 ◯270 158 2.7 Example 2 9.1 15 ◯ 315 164 2.6 Example 3 10.3 19 ◯ 256 1622.6 Example 4 9.9 18 ◯ 302 160 2.8 Example 5 10.4 22 ◯ 265 157 2.9Comparative 10.7 4.7 X 810 120 2.6 Example 1 Comparative 9.6 3 X 987 1222.4 Example 2 Comparative 10.0 3.7 X 867 125 2.6 Example 3 Comparative9.6 16 ◯ 310 163 1.7 Example 4

As shown in Table 3, the resin compositions for a semiconductor packageof the examples, and the prepregs and the copper clad laminates obtainedtherefrom, had a coefficient of thermal expansion of 9.1 to 10.5 ppm/°C., indicating low thermal expansion characteristics, and the minimumviscosity thereof was measured to be 256 to 315 Pa·s in a temperaturerange of 157 to 164° C., while the resin flow could be as high as 15 to23%, thereby ensuring excellent miscibility. In addition, themeasurement results of the tensile elongation showed high toughness of2.6 to 2.9%, thereby realizing excellent mechanical properties.

On the other hand, the resin compositions for a semiconductor package ofComparative Examples 1 to 3 not containing amine curing agents having anelectron withdrawing group (EWG), and the prepregs and the copper cladlaminates obtained therefrom exhibited the minimum viscosity of 810 to987 Pa·s in a temperature range of 120 to 125° C., which issignificantly higher than those of the examples, and showed extremelylow resin flow of 3 to 4.7%, indicating that the miscibility such as theoccurrence of the separation between the resin and the inorganic filleris remarkably poor.

On the other hand, it was confirmed that the resin compositions for asemiconductor package of Comparative Example 4 in which thethermosetting resin was contained in an amount of 625 parts by weightbased on 100 parts by weight of the amine curing agent and the ratio ofthe amine curing agent equivalent weight to the thermosetting resinequivalent weight was 0.63, and the prepreg and the copper clad laminateobtained therefrom had tensile elongation of 1.7%, which was decreasedas compared to those of the examples, indicating that there was a limitin toughness.

Accordingly, when the thermosetting resin was contained in an amount of400 parts by weight or less relative to 100 parts by weight of the aminecuring agent having an electron withdrawing group (EWG), and two typesof the inorganic fillers were mixed and used, while satisfying the ratioof the amine curing agent equivalent weight to the thermosetting resinequivalent weight of 1.4 or more, as in the examples, it was confirmedthat excellent low thermal expansion characteristics, flow properties,mechanical properties, and miscibility could be secured.

1. A resin composition comprising: an amine curing agent containing oneor more functional groups selected from the group consisting of asulfone group, a carbonyl group, a halogen group, an alkyl group having1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, aheteroaryl group having 2 to 30 carbon atoms, and an alkylene grouphaving 1 to 20 carbon atoms; a thermosetting resin; and an inorganicfiller comprising a first inorganic filler having an average particlediameter of 0.1 μm to 100 μm, and a second inorganic filler having anaverage particle diameter of 1 nm to 90 nm, wherein the thermosettingresin is present in an amount of 400 parts by weight or less based on100 parts by weight of the amine curing agent, and the alkyl grouphaving 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms,the heteroaryl group having 2 to 30 carbon atoms, and the alkylene grouphaving 1 to 20 carbon atoms contained in the amine curing agent are eachindependently substituted with one or more functional groups selectedfrom the group consisting of a nitro group, a cyano group, and a halogengroup.
 2. The resin composition of claim 1, wherein an equivalent ratiocalculated by the following Mathematical Equation 1, is 1.4 or more:Equivalent ratio=Total active hydrogen equivalent weight contained inthe amine curing agent/Total curable functional group equivalent weightcontained in the thermosetting resin.  [Mathematical Equation 1]
 3. Theresin composition of claim 1, wherein the amine curing agent includesone or more compounds selected from the group consisting of thefollowing Chemical Formulas 1 to 3:

wherein, in Chemical Formula 1, A is a sulfone group, a carbonyl group,or an alkylene group having 1 to 10 carbon atoms, X₁ to X₈ are eachindependently a nitro group, a cyano group, a hydrogen atom, a halogengroup, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,R₁, R₁′, R₂, and R₂′ are each independently a hydrogen atom, a halogengroup, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, nis an integer of 1 to 10, and the alkylene group having 1 to 10 carbonatoms, the alkyl group having 1 to 6 carbon atoms, the aryl group having6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbonatoms are each independently substituted with one or more functionalgroups selected from the group consisting of a nitro group, a cyanogroup, and a halogen group;

wherein, in Chemical Formula 2, Y₁ to Y₈ are each independently a nitrogroup, a cyano group, a hydrogen atom, a halogen group, an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms,or a heteroaryl group having 2 to 20 carbon atoms, R₃, R₃′, R₄, and R₄′are each independently a hydrogen atom, a halogen group, an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms,or a heteroaryl group having 2 to 20 carbon atoms, m is an integer of 1to 10, and the alkyl group having 1 to 6 carbon atoms, the aryl grouphaving 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20carbon atoms are each independently substituted with one or morefunctional groups selected from the group consisting of a nitro group, acyano group, and a halogen group;

wherein, in Chemical Formula 3, Z₁ to Z₄ are each independently a nitrogroup, a cyano group, a hydrogen atom, a halogen group, an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms,or a heteroaryl group having 2 to 20 carbon atoms, R₅, R₅′, R₆, and R₆′are each independently a hydrogen atom, a halogen group, an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms,or a heteroaryl group having 2 to 20 carbon atoms, and the alkyl grouphaving 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms,and the heteroaryl group having 2 to 20 carbon atoms are eachindependently substituted with one or more functional groups selectedfrom the group consisting of a nitro group, a cyano group, and a halogengroup.
 4. The resin composition of claim 1, wherein the inorganic filleris contained in an amount of 200 parts by weight or more based on 100parts by weight of the amine curing agent and the thermosetting resin.5. The resin composition of claim 1, wherein the inorganic filler ispresent in an amount of 200 parts by weight to 500 parts by weight,based on 100 parts by weight of the amine curing agent and thethermosetting resin.
 6. The resin composition of claim 1, wherein thesecond inorganic filler having an average particle diameter of 1 nm to90 nm is present in an amount of 1 part by weight to 50 parts by weight,based on 100 parts by weigh of the first inorganic filler having anaverage particle diameter of 0.1 μm to 100 μm.
 7. The resin compositionof claim 1, wherein the surface of the first inorganic filler having anaverage particle diameter of 0.1 μm to 100 μm, or the second inorganicfiller having an average particle diameter of 1 nm to 90 nm, is treatedwith a silane compound.
 8. The resin composition of claim 7, wherein thesilane compound includes one or more silane coupling agents selectedfrom the group consisting of an aminosilane coupling agent, an epoxysilane coupling agent, a vinyl silane coupling agent, a cationic silanecoupling agent, and a phenylsilane coupling agent.
 9. The resincomposition of claim 1, wherein the thermosetting resin includes one ormore resins selected from the group consisting of an epoxy resin, abismaleimide resin, a cyanate ester resin, and a bismaleimide-triazineresin.
 10. The resin composition of claim 1, wherein the inorganicfiller is dispersed in the resin composition.
 11. The resin compositionof claim 1, wherein the resin composition has a minimum viscosity at140° C. or higher, and a minimum viscosity of 100 Pa·s to 500 Pa·s. 12.The resin composition of claim 1, wherein the resin composition for hastensile elongation of 2.0% or more, as measured by IPC-TM-650(2.4.18.3).
 13. A prepreg obtained by impregnating a fiber substratewith the resin composition according to claim
 1. 14. A metal cladlaminate comprising the prepreg according to claim 13, and a metal foilintegrated with the prepreg by heating and pressurizing.